US8367796B2 - Catalytic polymerization of polymers containing electrophilic linkages using nucleophilic reagents - Google Patents
Catalytic polymerization of polymers containing electrophilic linkages using nucleophilic reagents Download PDFInfo
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- 0 *N=C(N(*)*)N(*)* Chemical compound *N=C(N(*)*)N(*)* 0.000 description 11
- BPTAHCGWSQSDSL-VSBWTOFMSA-N C1=CC=C([C@H]2CN3C[C@H](C4=CC=CC=C4)NC3=N2)C=C1.C1CN2CCNC2=N1.C1CN=C2NCCCN2C1.C1CN=C2NCCN2C1 Chemical compound C1=CC=C([C@H]2CN3C[C@H](C4=CC=CC=C4)NC3=N2)C=C1.C1CN2CCNC2=N1.C1CN=C2NCCCN2C1.C1CN=C2NCCN2C1 BPTAHCGWSQSDSL-VSBWTOFMSA-N 0.000 description 1
- YVJMFNLTUJIINW-UHFFFAOYSA-N C1CCC(/N=C(/NC2CCCCC2)N2CCCC2)CC1 Chemical compound C1CCC(/N=C(/NC2CCCCC2)N2CCCC2)CC1 YVJMFNLTUJIINW-UHFFFAOYSA-N 0.000 description 1
- SSZYMHGOBFBYIT-UHFFFAOYSA-N C1CCC(/N=C(/NC2CCCCC2)N2CCCN3CCCN=C32)CC1 Chemical compound C1CCC(/N=C(/NC2CCCCC2)N2CCCN3CCCN=C32)CC1 SSZYMHGOBFBYIT-UHFFFAOYSA-N 0.000 description 1
- SOROMHWGAVHFSE-UHFFFAOYSA-N C1CN=C2NCCCN2C1.COC(=O)C1=CC=C(C(=O)OC)C=C1.O=C(OCCO)C1=CC=C(C(=O)OCCO)C=C1.O=C(OCCO)C1=CC=C(C(=O)OCCO)C=C1.OCCO Chemical compound C1CN=C2NCCCN2C1.COC(=O)C1=CC=C(C(=O)OC)C=C1.O=C(OCCO)C1=CC=C(C(=O)OCCO)C=C1.O=C(OCCO)C1=CC=C(C(=O)OCCO)C=C1.OCCO SOROMHWGAVHFSE-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N CC Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YHOUNRDQQCOLBQ-NDEPHWFRSA-N OC(C1=CC=CC=C1)(C1=CC=CC=C1)[C@@H]1CCCN1/C(=N\C1CCCCC1)NC1CCCCC1 Chemical compound OC(C1=CC=CC=C1)(C1=CC=CC=C1)[C@@H]1CCCN1/C(=N\C1CCCCC1)NC1CCCCC1 YHOUNRDQQCOLBQ-NDEPHWFRSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
Definitions
- This invention relates generally to the polymerization of monomers, and, more particularly relates to an organocatalytic method for polymerizing monomers.
- the invention is applicable in numerous fields, including industrial chemistry and manufacturing processes requiring a simple and convenient method for the preparation of polymers.
- PET poly(ethylene terephthalate)
- PET poly(oxy-1,2-ethanediyl-oxycarbonyl-1,4-diphenylenecarbonyl
- Polymers with heteroatoms along the backbone are commonly prepared using an addition-type polymerization mechanism, in which monomers react to form dimers, which can in turn react with other dimers to form tetramers. This growth process is allowed to continue until polymers with the desired molecular weight are formed. Unfortunately (and unlike the alternative chain-growth polymerization mechanism), obtaining high molecular weight polymer using this mechanism requires carrying the polymerization reaction to very high conversion.
- a frequently-used method for commercial synthesis of (PET) involves a two-step transesterification process from dimethyl teraphthalate (DMT) and excess ethylene glycol (EO) in the presence of a metal alkanoates or acetates of calcium, zinc, manganese, titanium, etc.
- This first step generates bis(hydroxy ethylene) teraphthalate (BHET) with the elimination of methanol and the excess EO.
- the BHET is heated, generally in the presence of a transesterification catalyst, to generate high polymer.
- This process is generally accomplished in a vented extruder to remove the polycondensate (EO) and generate the desired thermoformed object from a low viscosity precursor.
- Some polycondensation reactions such as the commercial method of synthesis of PET described above, require polymerization catalysts.
- Such catalysts may be difficult to prepare, may be unstable to long-term storage, or may require stringent reaction conditions to provide polymer.
- these catalyst are immortal, limiting the versatility of the widely used mechanical recycling, because at high temperatures the residual catalyst cause molecular weight degradation. This limits the use of these recycled products to secondary applications (i.e., carpet, playground equipment etc.).
- the invention provides an efficient catalytic polymerization reaction that does not employ a metallic catalyst. Because a nonmetallic catalyst is employed, the polymerization products, in a preferred embodiment, are substantially free of metal contaminants. Furthermore, in preferred embodiments, the catalysts are substantially more stable than previous non-metallic catalysts.
- the disclosure provides a method for forming a polymer.
- the method comprises contacting a monomer with a nucleophilic reagent in the presence of a guanidine-containing compound to form a prepolymer.
- the method further comprises polymerizing the prepolymer to form a polymer.
- the monomer comprises at least one electrophilic moiety, and in some embodiments, the monomer comprises two electrophilic moieties separated by a linker.
- the disclosure provides a composition
- a composition comprising a monomer, a nucleophile, and a guanidine-containing compound.
- the monomer comprises two electrophilic moieties separated by a linker.
- the disclosure provides an improved method for polymerizing a monomer having at least one electrophilic moiety.
- the improvement comprises contacting the monomer with a nucleophile in the presence of a guanidine-containing compound.
- Preferred catalysts herein are guanidine compounds.
- cyclic guanidines including monocyclic and polycyclic guanidines are used.
- Polycyclic guanidines suitable for the methods of the disclosure include fused and non-fused polycyclic compounds. Further details of suitable guanidine catalysts are provided below.
- this invention is not limited to specific polymers, catalysts, nucleophilic reagents, or depolymerization conditions.
- the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
- a polymer encompasses a combination or mixture of different polymers as well as a single polymer
- a catalyst encompasses both a single catalyst as well as two or more catalysts used in combination, and the like.
- alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group (i.e., a mono-radical) typically although not necessarily containing 1 to about 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.
- alkyl groups herein may contain 1 to about 18 carbon atoms, and such groups may contain 1 to about 12 carbon atoms.
- lower alkyl intends an alkyl group of 1 to 6 carbon atoms. “Substituted alkyl” refers to alkyl substituted with one or more substituent groups, and this includes instances wherein two hydrogen atoms from the same carbon atom in an alkyl substituent are replaced, such as in a carbonyl group (i.e., a substituted alkyl group may include a —C( ⁇ O)-moieity).
- heteroatom-containing alkyl and “heteroalkyl” refer to an alkyl substituent in which at least one carbon atom is replaced with a heteroatom, as described in further detail infra. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl or lower alkyl, respectively.
- alkenyl refers to a linear, branched or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
- alkenyl groups herein may contain 2 to about 18 carbon atoms, and for example may contain 2 to 12 carbon atoms.
- lower alkenyl intends an alkenyl group of 2 to 6 carbon atoms.
- substituted alkenyl refers to alkenyl substituted with one or more substituent groups
- heteroatom-containing alkenyl and heteroalkenyl refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
- alkynyl refers to a linear or branched hydrocarbon group of 2 to 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Generally, although again not necessarily, alkynyl groups herein may contain 2 to about 18 carbon atoms, and such groups may further contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms.
- substituted alkynyl refers to alkynyl substituted with one or more substituent groups
- heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
- alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as —O-alkyl where alkyl is as defined above.
- a “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms, and includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, t-butyloxy, etc.
- Substituents identified as “C 1 -C 6 alkoxy” or “lower alkoxy” herein may, for example, may contain 1 to 3 carbon atoms, and as a further example, such substituents may contain 1 or 2 carbon atoms (i.e., methoxy and ethoxy).
- alkylthio refers to a group —S-alkyl, where “alkyl” is as defined above.
- aryl refers to an aromatic substituent generally, although not necessarily, containing 5 to 30 carbon atoms and containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
- Aryl groups may, for example, contain 5 to 20 carbon atoms, and as a further example, aryl groups may contain 5 to 12 carbon atoms.
- aryl groups may contain one aromatic ring or two or more fused or linked aromatic rings (i.e., biaryl, aryl-substituted aryl, etc.).
- aryl refers to an aryl moiety substituted with one or more substituent groups
- heteroatom-containing aryl and “heteroaryl” refer to aryl substituent, in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra. If not otherwise indicated, the term “aryl” includes unsubstituted, substituted, and/or heteroatom-containing aromatic substituents.
- aralkyl refers to an alkyl group with an aryl substituent
- alkaryl refers to an aryl group with an alkyl substituent, wherein “alkyl” and “aryl” are as defined above.
- aralkyl and alkaryl groups herein contain 6 to 30 carbon atoms.
- Aralkyl and alkaryl groups may, for example, contain 6 to 20 carbon atoms, and as a further example, such groups may contain 6 to 12 carbon atoms.
- alkylene refers to a di-radical alkyl group. Unless otherwise indicated, such groups include saturated hydrocarbon chains containing from 1 to 24 carbon atoms, which may be substituted or unsubstituted, may contain one or more alicyclic groups, and may be heteroatom-containing. “Lower alkylene” refers to alkylene linkages containing from 1 to 6 carbon atoms. Examples include, methylene (—CH 2 —), ethylene (—CH 2 CH 2 —), propylene (—CH 2 CH 2 CH 2 —), 2-methylpropylene (—CH 2 —CH(CH 3 )—CH 2 —), hexylene (—(CH 2 ) 6 —) and the like.
- alkenylene alkynylene
- arylene aralkylene
- alkarylene alkarylene
- linkers di-radical alkenyl, alkynyl, aryl, aralkyl, and alkaryl groups, respectively.
- linkers Collectively, these and other di-radical groups are referred to herein as “linkers” or “linker groups.”
- linker group or “functional linker” is meant di-radical moieties that contain one or more functional groups such as an oxo (—O—, such as in an ether linkage), amine (—NR—), carbonyl (—C( ⁇ O)—), carbonate, and the like.
- amino is used herein to refer to the group —NZ 1 Z 2 wherein Z 1 and Z 2 are hydrogen or nonhydrogen substituents, with nonhydrogen substituents including, for example, alkyl, aryl, alkenyl, aralkyl, and substituted and/or heteroatom-containing variants thereof.
- halo and “halogen” are used in the conventional sense to refer to a chloro, bromo, fluoro or iodo substituent.
- heteroatom-containing refers to a molecule, linkage or substituent in which one or more carbon atoms are replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
- heteroalkyl refers to an alkyl substituent that is heteroatom-containing
- heterocyclic refers to a cyclic substituent that is heteroatom-containing
- heteroaryl and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
- heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.
- heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, furyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.
- heteroatom-containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, tetrahydrofuranyl, etc.
- Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, including 1 to about 24 carbon atoms, further including 1 to about 18 carbon atoms, and further including about 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
- Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
- heteroatom-containing hydrocarbyl refers to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” is to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl moieties.
- hydrocarbylene refers to a di-radical hydrocarbyl group.
- substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
- substituents include, without limitation: functional groups such as halo, hydroxyl, sulfhydryl, C 1 -C 24 alkoxy, C 2 -C 24 alkenyloxy, C 2 -C 24 alkynyloxy, C 5 -C 20 aryloxy, acyl (including C 2 -C 24 alkylcarbonyl (—CO-alkyl) and C 6 -C 20 arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl), C 2 -C 24 alkoxycarbonyl (—(CO)—O-alkyl), C 6 -C 20 aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C 2 -C 24 alkylcarbonato (—O—(CO)—O-alkyl), C 6 -C 20 arylcarbonato (—O—(CO)—O-aryl), carboxy
- the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
- the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
- the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
- the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
- substituted When the term “substituted” appears prior to a list of possible substituted groups, it is intended that the term apply to every member of that group. For example, the phrase “substituted alkyl and aryl” is to be interpreted as “substituted alkyl and substituted aryl.”
- reference to an atom is meant to include isotopes of that atom.
- reference to H is meant to include 1 H, 2 H (i.e., D) and 3 H (i.e., T)
- reference to C is meant to include 12 C and all isotopes of carbon (such as 13 C).
- substantially free of a particular type of chemical compound is meant that a composition or product contains less 10 wt % of that chemical compound, for example less than 5 wt %, or less than 1 wt %, or less than 0.1 wt %, or less than 0.01 wt %, or less than 0.001 wt %.
- the polymerization product herein is “substantially free of” metal contaminants, including metals per se, metal salts, metallic complexes, metal alloys, and organometallic compounds.
- guanidine compound refers to compounds containing a guanidinyl moiety, i.e., compounds containing the structure
- the electrophilic linkages may be, for example, ester linkages (—(CO)—O—), carbonate linkages (—O—(CO)—O)—, urethane linkages (—O—(CO)—NH), substituted urethane linkages (—O—(CO)—NR—, where R is a nonhydrogen substituent such as alkyl, aryl, alkaryl, or the like), amido linkages (—(CO)—NH—), substituted amido linkages (—(CO)—NR—where R is as defined previously), thioester linkages (—(CO)—S—), sulfonic ester linkages (—S(O) 2 —O—), ketone linkages (—C( ⁇ O)—), and the like.
- Other electrophilic linkages will be known to those of ordinary skill in the art of organic chemistry and polymer science and/or can be readily found by
- the monomer comprises two electrophilic moieties separated by a linker moiety, and has the structure X 1 -L-X 2 , wherein X 1 and X 2 are independently electrophilic moieties and L is the linker moiety.
- L is selected from C 1 -C 30 hydrocarbylene and functional linker groups. In some embodiments, L is C 1 -C 30 hydrocarbylene.
- L is selected from C 1 -C 30 alkylene, C 2 -C 30 alkenylene, C 2 -C 30 alkynylene, C 5 -C 30 arylene, and combinations thereof (such as C 1 -C 30 alkylene linked with a C 5 -C 30 arylene), wherein any of these groups may contain one or more heteroatoms and one or more substituents.
- Linker moieties may also be functional groups, such as heteroatom groups, including thioether (—S—), ether (—O—), and amino (—NR—) groups.
- L is substituted or unsubstituted phenylene (1,4-, 1,3-, or 1,2-connectivity), or substituted or unsubstituted lower alkylene (e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, septylene, or octylene, including cyclic versions of such linkers).
- substituted or unsubstituted phenylene (1,4-, 1,3-, or 1,2-connectivity
- substituted or unsubstituted lower alkylene e.g., methylene, ethylene, propylene, butylene, pentylene, hexylene, septylene, or octylene, including cyclic versions of such linkers.
- X 1 and X 2 are independently selected from ester moieties (—(CO)—O—R, wherein R is lower alkyl or the like), carboxylic acid or carbonic acid (—COOH or —OCOOH), carbonate moieties (—O—(CO)—O—R, wherein R is lower alkyl or the like), urethane moieties (—O—(CO)—NH—R, wherein R is H, lower alkyl, or the like), substituted urethane moieties (—O—(CO)—NR′—R, where R′ is a nonhydrogen substituent such as alkyl, aryl, alkaryl, or the like), amido moieties (—(CO)—NH—R, wherein R is H, lower alkyl, or the like), substituted amido moieties (—(CO)—NR′—R where R′ is as defined previously), thioester moieties (—(CO)—S—R, wherein R is H,
- poly(alkylene terephthalates) such as poly(ethylene terephthalate) (PET), fiber-grade PET (a homopolymer made from monoethylene glycol and terephthalic acid), bottle-grade PET (a copolymer made based on monoethylene glycol, terephthalic acid, and other comonomers such as isophthalic acid, cyclohexene dimethanol, etc.), poly(butylene terephthalate) (PBT), and poly(hexamethylene terephthalate); poly(alkylene adipates) such as poly(ethylene adipate), poly(1,4-butylene adipate), and poly(hexamethylene adipate); poly(alkylene suberates) such as poly(ethylene suberate); poly(alkylene sebacates) such as poly(ethylene sebacate); poly( ⁇ -caprolactone) and poly( ⁇ -propiolactone); poly(alkylene terephthalates) such as poly(ethylene terephthalate)
- the monomers for polymerization may be obtained from any suitable source.
- the monomers are depolymerization products from recycled post-consumer waste.
- the monomers are virgin feedstock.
- Nucleophilic reagents are those that comprise one or more nucleophilic groups, such as hydroxyl, ether, carboxylato (e.g., —COO ⁇ ), amine, azide, sulfhydryl, and the like. Nucleophilic reagents therefore include monohydric alcohols, diols, polyols, amines, diamines, polyamines, sulfhydryls, disulfhydryls, polysulfhydryls, and combinations thereof. Thus, the nucleophilic reagents may contain a single nucleophilic moiety or two or more nucleophilic moieties, e.g., hydroxyl, sulfhydryl, and/or amino groups.
- the nucleophilic reagent consists of a single nucleophilic group, and has the structure R-Nu 1 , wherein R is a C 1 -C 30 hydrocarbyl group and Nu 1 is any nucleophilic group such as those previously described.
- nucleophilic reagents comprise two nucleophilic groups separated by a linker, and have the structure Nu 1 -L 1 -Nu 2 , wherein Nu 1 is as described previously, Nu 2 is a nucleophilic group (such as those described for Nu 1 ) and wherein L 1 is as described previously for L.
- difunctional nucleophilic reagents include alkyl diols, aryl diols, alkyl diamines, aryl diamines, amino alcohols, amino thiols, and the like.
- the nucleophilic reagent comprises three nucleophilic groups, and has the structure
- nucleophilic reagents allows cross linking reactions to occur. Any combination of nucleophilic reagents (having the same or a different number of nucleophilic groups) may be used.
- the nucleophilic reagent will be present in excess of the monomer, meaning that the number of nucleophilic groups exceeds the number of electrophilic groups at the beginning of the reaction. In some other embodiments, the ratio of nucleophilic groups to electrophilic groups is 1:1.
- nucleophilic groups include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, methylamine, ethylamine, ethylenediamine, propylenediamine, methanethiol, ethanethiol, as well as the following:
- Preferred catalysts for the polymerization reactions are organic compounds containing a guanidine moiety.
- the polymerization catalysts are organic guanidines having the structure of formula (I)
- R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen and C 1 -C 30 hydrocarbyl, provided that any two of R 2 , R 3 , R 4 and R 5 may be linked to form a cycle. In preferred embodiments, at least two of R 2 , R 3 , R 4 and R 5 are linked to form a cycle, such that the compound is a cyclic guanidine compound.
- R 2 , R 3 , R 4 and R 5 are independently selected from substituted or unsubstituted C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 5 -C 30 aryl, C 6 -C 30 aralkyl, and C 6 -C 30 alkaryl, any of which may be heteroatom-containing.
- the alkyl, alkenyl, and alkynyl groups include linear, branched, and cyclic such groups.
- the aryl, aralkyl, and alkaryl groups include multicyclic groups such as annulated and linked ring systems.
- R 2 and R 3 are taken together to form a cycle, and R 4 and R 5 are taken together to form a cycle, such that an annulated ring system is formed.
- Preferred embodiments include compounds having the structure of formula (Ia)
- n1 and n2 are independently selected from zero and 1;
- R 6a , R 6b , R 6c , R 6d , R 7a , R 7b , R 7c , and R 7d are independently selected from H, substituted or unsubstituted C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 5 -C 30 aryl, C 6 -C 30 aralkyl, and C 6 -C 30 alkaryl, any of which may be may be heteroatom-containing, provided that any two of R 6a , R 6b , R 6c , R 6d , R 7a , R 7b , R 7c , and R 7d may be taken together to form a ring.
- n1 is zero and n2 is 1. In some embodiments of formula (Ia), n2 is zero and n1 is 1. In some embodiments of formula (Ia), n1 and n2 are both zero. In some embodiments of formula (Ia), n1 and n2 are both 1.
- one of R 6a and R 6b is C 5 -C 30 aryl, and the other is Hydrogen, and one of R 7a and R 7b is C 5 -C 30 aryl, and the other is H.
- the C 5 -C 30 aryl group is phenyl.
- R 6c , R 6d , R 7c , and R 7d are each H. Examples of such embodiments include the following compounds:
- R 3 and R 4 are taken together to form a cycle.
- preferred embodiments include compounds having the structure of formula (Ib)
- n3 is selected from 0 and 1;
- X 1 and X 2 are independently selected from —NR 10 — and —C(R 11 )(R 12 )—, wherein R 10 , R 11 , and R 12 are independently selected from H and alkyl; and
- R 8a , R 8b , R 9a , and R 9b are independently selected from alkyl, aryl, aralkyl, and alkaryl, provided that any two of R 8a , R 8b , R 9a , R 9b , R 10 , R 11 , and R 12 may be taken together to form a cycle.
- R 9a and R 9b are both H, and X 1 and X 2 are both —CH 2 —, such that the compounds have the structure of formula (Ic)
- R 2 and R 5 are independently selected from substituted or unsubstituted C 1 -C 30 alkyl and substituted or unsubstituted heteroatom-containing C 1 -C 30 alkyl.
- R 2 and R 5 may be C 3 -C 30 alicyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl (Cy), cycloheptyl, or cyclooctyl.
- R 2 and R 5 may be methyl, ethyl, propyl (i-propyl, n-propyl), or butyl (t-butyl, n-butyl, sec-butyl), or may be heteroatom-containing such as 3-dimethylaminopropyl or a salt thereof.
- the guanidine-containing compounds described herein are chemically more stable than other catalysts capable of causing depolymerization, such as N-heterocyclic carbene catalysts.
- the guanidine-containing compounds decompose at a substantially lower rate.
- Preferred catalysts are substantially stable under some or all of the depolymerization conditions described herein.
- guanidine-containing compounds described herein may be synthesized by any appropriate method, and such methods are readily ascertainable from the relevant literature.
- cyclic guanidines may be prepared using the methods disclosed in U.S. Pat. No. 4,797,487, “Production of Bicyclic Guanidines from Bis(aminoalkyl)amine.” It will be appreciated that the handling of certain guanidine-containing compounds may require precautions to avoid decomposition. For example, mixing of the reaction components may require an inert atmosphere.
- the polymerization catalysts of the disclosure are typically present in the reaction mixture in an amount (i.e., a “catalyst loading”) that is less than 5 mol %, or less than 2 mol %, or less than 1 mol %, or less than 0.5 mol %, or less than 0.1 mol %, with less than 1 mol % being particularly preferred.
- a “catalyst loading” is measured as mol % relative to the total amount of monomer used in the reaction.
- the polymerization reaction occurs by initial formation of a prepolymer comprising the product of a reaction between the monomer and nucleophilic reactant, and subsequent condensation polymerization of the prepolymer.
- the prepolymer comprises one or more electrophilic groups and one or more nucleophilic groups; for example the prepolymer comprises two nucleophilic groups and two electrophilic groups.
- the condensation reaction may occur as the electrophilic group of one prepolymer molecule react with the nucleophilic group of another prepolymer molecule.
- condensation reaction produces non-polymeric byproducts (particularly small organic molecules such as water, H 2 , ethylene glycol, propylene glycol, etc.), such products may be removed during the reaction to help the polymerization achieve higher molecular weight polymers.
- the initial formation of the prepolymer may be carried out in a suitable solvent, or without any solvent.
- the nucleophilic reagent may function as a solvent.
- the polymerization reaction is started in a solvent for a predetermined period of time, after which time the solvent is removed (such as by applying reduced pressure and/or increased temperature), and the polymerization is allowed to continue for a period of time sufficient to provide polymer of the desired molecular weight.
- the polymerization reaction may be carried out in an inert atmosphere.
- combination of the reactants may be accomplished in any order.
- the reactants can be combined by dissolving a catalytically effective amount of the selected catalyst in a solvent, combining the monomer and the catalyst solution, and then adding the nucleophilic reagent.
- the monomer, the nucleophilic reagent, and the catalyst are combined and dissolved in a suitable solvent, and polymerization thus occurs in a one-pot, one-step reaction.
- the reaction mixture is typically, although not necessarily, agitated (e.g., stirred), and the progress of the reaction can be monitored by standard techniques, although visual inspection is generally sufficient.
- solvents that may be used in the polymerization reaction include organic, protic, or aqueous solvents that are inert under the polymerization conditions, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, or mixtures thereof.
- Preferred solvents include toluene, methylene chloride, tetrahydrofuran, methyl t-butyl ether, Isopar, gasoline, and mixtures thereof.
- Reaction temperatures are in the range of about 25° C. to about 300° C.
- the total polymerization reaction time will generally, although again not necessarily, be in the range of about 1 to 24 hours.
- the reactions are carried out by first combining the monomer with the nucleophilic reagent and the catalyst in a solvent. After allowing sufficient time for the monomer to react with the nucleophilic reagent to form a prepolymer, the reaction conditions are changed to encourage polymerization of the prepolymer. For example, elevated temperature and/or reduced pressure may be applied in order to force the condensation of prepolymer molecules. In some embodiments, the temperature of the reaction after formation of the prepolymer is raised to between 100° C. and 200° C., or greater than about 150° C., or greater than about 170° C.
- the amount of time required to form the prepolymer from the monomer and the nucleophilic reagent will vary depending upon the reactants and conditions, but may be estimated or determined by the usual analytical methods.
- the temperature during formation of the prepolymer may be room temperature or higher, for example between 30° C. and 100° C.
- the polymerization product from reactions according to the invention contain product polymer and the guanidine-containing catalyst, which may be removed from the polymer product in the usual manner.
- the methods of the disclosure allow for the polymerization of a monomer starting material to provide a polymerization product that is substantially free of metal contaminants.
- the concentration of metal contaminants in the polymer products is equal to or less than the concentration of metal contaminants in the starting materials prior to polymerization.
- the polymerization reaction according to the invention does not increase the total concentration of metal contaminants.
- the polymer products e.g., PET
- a lower concentration of metal contaminant may be observed if the polymer products are subjected to any purification steps (such as precipitation, filtration, etc.).
- a sample of DMT having no metal contaminants (or an undetectable level of metal contaminants) may be polymerized according to the invention to yield polymer products having no metal contaminants (or an undetectable level of metal contaminants).
- the polymerization reactions of the disclosure allow preparation of polymer products having a metal contaminant concentration that is immeasurable, or equal to or less than the metal contaminant concentration of the starting materials used to prepare the polymer.
- Such polymer products may have substantially less metal contaminant concentrations than similar polymers prepared using conventional (i.e., metal catalyzed) polymerization methods.
- conventional PET used for drinking bottles may have a residual metal contamination level of up to 50 ppm, or up to 20 ppm, or up to 5 ppm.
- the methods of the invention provide PET suitable for food and beverage storage since the level of metal contamination of the polymerization products will be no higher than the level of metal contamination of the original monomer.
- the methods of the invention provide polymers having a metal contamination concentration of ⁇ 50 ppm, or ⁇ 20 ppm, or ⁇ 5 ppm, or below 1 ppm.
- the methods described herein find utility, for example, in the preparation of polymers and items made from polymers, the use of recycled polymer depolymerization products, and similar areas as described herein throughout.
- Sample 1 is a PET that was polymerized (bulk) with 2 mol % of catalysts relative to DMT. Since the concentration of ethylene glycol tends to vary during the course of the polymerization, all catalysts loadings are relative to dimethyl terephthalate (DMT). The maximum polymerization temperature in the case was 200° C.
- Sample 2 was also PET that was polymerized with 1.5 mol % catalyst relative to DMT.
- the maximum polymerization temperature in this case was 275° C.
- the product polymers were characterized by 1 H NMR.
- DCC was reacted neat (110° C.) with a secondary amine. Once the DCC melted a homogeneous solution was formed and the reaction was allowed to proceed overnight to generate a viscous oil/gel. The reaction was followed by GC/MS and quantitative conversion of starting material was accomplished in ⁇ 12 hours. Compounds were purified either by kugelroh distillation or by column chromatography.
Abstract
Description
(also written Nu1-L3(Nu2)Nu3) wherein Nu1 and Nu2 are as described previously, Nu3 is a nucleophilic group (such as those described for Nu1), and L3 may be any of the linkers described previously for L1, provided that linker L3 has at least three non-hydrogen substituents (i.e., Nu1-Nu3). Such nucleophilic reagents allows cross linking reactions to occur. Any combination of nucleophilic reagents (having the same or a different number of nucleophilic groups) may be used.
DCC was reacted neat (110° C.) with a secondary amine. Once the DCC melted a homogeneous solution was formed and the reaction was allowed to proceed overnight to generate a viscous oil/gel. The reaction was followed by GC/MS and quantitative conversion of starting material was accomplished in ˜12 hours. Compounds were purified either by kugelroh distillation or by column chromatography.
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